CN104201358A - Carbon-sulfur composite positive electrode wrapped by nano-polyaniline and preparation method of carbon-sulfur composite positive electrode - Google Patents
Carbon-sulfur composite positive electrode wrapped by nano-polyaniline and preparation method of carbon-sulfur composite positive electrode Download PDFInfo
- Publication number
- CN104201358A CN104201358A CN201410502622.4A CN201410502622A CN104201358A CN 104201358 A CN104201358 A CN 104201358A CN 201410502622 A CN201410502622 A CN 201410502622A CN 104201358 A CN104201358 A CN 104201358A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- composite
- nano
- sulfur
- vertical orientated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a carbon-sulfur composite positive electrode wrapped by nano-polyaniline for a secondary aluminum battery. The positive electrode is prepared by compounding vertical alignment graphene, nano-polyaniline and a sulfur-containing active substance and is provided with a continuous three-dimensional conductive framework; in a preparation process, a conductive agent and an adhesive do not need to be added; the working procedures are simple, the cost is low, and the energy density is high; the carbon-sulfur composite positive electrode is applied to a secondary aluminum battery system, so that the specific capacity, the stability and the cyclicity of the battery are effectively improved.
Description
Technical field
The invention belongs to battery material scientific domain, relate to a kind of secondary aluminium cell anode composite, relate in particular to coated carbon sulphur anode composite of a kind of nano polyaniline and preparation method thereof.The invention still further relates to a kind of secondary aluminium cell of this anode composite of application.
Background technology
The develop rapidly of the new energy technologies such as regenerative resource is grid-connected, electric automobile and intelligent grid is in the urgent need to developing the more energy storage system of high-energy-density.Secondary aluminium-sulfur battery, as emerging battery system, is taking metallic aluminium as negative pole, and sulphur or sulfur-based compound are anodal battery system, have the features such as aboundresources, pollution-free, cheap, energy density is high, use is safe.The theoretical volume specific capacity of aluminium is 8050mAh/cm
3, be 4 times of lithium, and chemical activity is stable, be desirable negative material, and the theoretical volume specific capacity of sulphur is 3467mAh/cm
3, be one of positive electrode that known energy density is the highest.But, the dissolving in organic electrolyte due to the nonconducting natural quality of elemental sulfur and electric discharge intermediate product, easily cause the utilance of active material low, electrode passivation, the capacity loss of battery, the problems such as cycle performance is poor, one of approach of solution is with to have carbon-based material and conducting polymer materials that confinement effect, adsorption effect and conductivity are high compound by sulfur-bearing active material.
Graphene is a kind of carbon element class material of accurate Colloidal particles, the great specific area having, and the conductivity of superelevation and outstanding heat conductivility, be one of desirable energy storage material.But, because Graphene is very easily reunited, this has reduced its surface area as electrode material to a great extent, its actual specific area and the performance as active ingredient carriers are seriously reduced, not only make electrolyte be difficult to fully contact with Graphene surface, and the adsorbance of active material is few, utilance is low.
Polyaniline has that the ability of electric charge of storage is high, chemical property is good, density is little, low cost and other advantages, and there is reversible oxidation/reduction characteristic, in composite electrode, not only can be used as conductive matrices but also can be used as active material, be widely used in electrode material.But in doping/dedoping process, may expand and shrink, reduce the cycle life of battery.
Summary of the invention
(1) goal of the invention
For addressing the above problem and deficiency, the carbon sulphur anode composite that provides a kind of nano polyaniline coated is provided the object of the invention, and wherein Graphene vertically grows in conductive substrates, is three-dimensional net structure, as the conducting matrix grain of electrode, be compounded with polyaniline and the sulfur-bearing active material of nanostructure therebetween.
Described anode composite can be given full play to the excellent specific property of Graphene itself, compare unordered stacking Graphene, the orderly laminated structure of vertical orientated Graphene and open bore structure, the advantage such as have that specific surface is huge, absorption affinity is strong, good stability, electronics shift and charge transfer is fast.With polyaniline compound tense, polyaniline is uniformly distributed in order with nano shape in three-dimensional network skeleton, closely compound with carbon back skeleton, further strengthens its conductivity.In the process of composite sulfur, polyaniline can closely be bonded in sulphur on conducting matrix grain, the network configuration of nano-scale not only can provide more active material load byte simultaneously, the further fixing sulphur of absorption, sulphur is joined with conducting matrix grain on nanoscale, greatly promote activity and the utilance of sulphur, but also can fetter and suppress the dissolving of the intermediate products such as little molecular sulfur compound, thereby slow down the loss of sulphur.In addition, polyaniline can also be served as supplementing of active material, further promotes electrode capacity, and then promotes cell integrated efficiency for charge-discharge and cycle performance.Owing to having saved the interpolation of binding agent and conductive agent in electrode production process, can further improve the specific capacity of electrode.
The present invention also aims to provide the preparation method of the coated carbon sulphur anode composite of a kind of nano polyaniline.
The present invention also aims to provide a kind of secondary aluminium cell that comprises described anode composite.
(2) technical scheme
For achieving the above object, the present invention takes following technical scheme:
The carbon sulphur anode composite that nano polyaniline is coated, is characterized in that, comprising:
(a) vertical orientated Graphene;
(b) conductive substrates;
(c) nano polyaniline; With
(d) sulfur-bearing active material.
The coated carbon sulphur anode composite of nano polyaniline described in scheme, is characterized in that, Graphene is vertically grown in conductive substrates surface.
The coated carbon sulphur anode composite of nano polyaniline described in scheme, it is characterized in that, described conductive substrates includes but not limited to the metals or nonmetal such as carbon fiber, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon.
The coated carbon sulphur anode composite of nano polyaniline described in scheme, is characterized in that, described polyaniline is to be coated on vertical orientated Graphene surface with nanoscale.
The coated carbon sulphur anode composite of nano polyaniline described in scheme, is characterized in that the organic compound that described sulfur-bearing active material comprises elemental sulfur or contains S-S key.
The coated carbon sulphur anode composite of nano polyaniline described in scheme, is characterized in that, described sulfur-bearing active material is distributed in vertical orientated Graphene with nanoscale.
The coated carbon sulphur anode composite of nano polyaniline described in scheme, is characterized in that, comprises 60 ~ 80% sulphur, 15 ~ 30% polyaniline and 5 ~ 10% vertical orientated Graphene, and described is mass percentage content.
Scheme also provides the preparation method of the coated carbon sulphur anode composite of a kind of nano polyaniline, it is characterized in that, comprises the following steps:
Step 1, prepare vertical orientated Graphene: by plasma enhanced chemical vapor deposition at the vertical orientated Graphene of conductive substrates superficial growth;
Step 2, composite polyphenylene amine: configuration 0.5mol/L sulfuric acid solution, to the aniline monomer that adds 0.2mol/L in this solution, passes into nitrogen and stir stand-by; Then taking the orientation Graphene for preparing as work electrode, saturated calomel electrode is as reference electrode, platinum electrode are as to electrode, adopts cyclic voltammetry to prepare polyaniline, its potential range is 0.6V ~ 0.8V, reaction time 1h; Finally take out product, through distilled water flushing, dry, obtain vertical orientated Graphene-nano polyaniline composite material;
Step 3, composite sulfur: adopt heat treated mode that sulphur is carried in the prepared vertical orientated Graphene-nano polyaniline composite material of step 2.Particularly, by the vertical orientated graphene-polyaniline composite material preparing and sulfur-bearing active material in mass ratio 1:5 ~ 1:20 mix, under inert gas shielding, be heated to 155 ~ 300 DEG C and form the coated carbon sulphur anode composites of nano polyaniline; Or sulfur-bearing active material is heated to molten state, under inert gas shielding, the vertical orientated graphene-polyaniline composite material preparing is put into wherein, keep taking out after 5 ~ 10h that to put into baking oven dry, form the coated carbon sulphur anode composite of nano polyaniline.
Scheme also provides a kind of secondary aluminium cell that adopts above-mentioned anode composite, it is characterized in that, comprising:
(a) positive pole, the carbon sulphur anode composite that described just very nano polyaniline is coated;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
Secondary aluminium cell described in scheme also can comprise the barrier film between positive pole and negative pole.Suitable solid porous diaphragm material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.Described in scheme containing aluminium negative active core-shell material, include but not limited to: aluminum metal, for example aluminium foil and be deposited on the aluminium on base material; Aluminium alloy, comprises and contains at least one element of being selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and the alloy of Al.
Non-water described in scheme is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
In organic salt-aluminum halide system described in scheme, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl
-, Br
-, I
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
2]
-, [N (CN)
2]
-plasma.
Organic salt-aluminum halide system described in scheme, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
Described in scheme, the preparation method of secondary aluminium cell is as follows: by above-mentioned composite positive pole be cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, be wound into battery core with the thick barrier film of 0.16mm and the negative pole made as negative active core-shell material with aluminium flake and pack nickel plating box hat into, the electrolyte that reinjects, secondary aluminium cell is made in sealing.
(3) beneficial effect
The invention provides a kind of secondary aluminium cell that comprises the coated carbon sulphur anode composite of nano polyaniline.Described anode is to be vertically grown in orientation Graphene in conductive substrates as three-dimensional network conducting matrix grain, the polyaniline of composite Nano size and sulfur-bearing active material therebetween.This electrode preparation section is easy, with low cost, and without additional conductive agent and binding agent, doubly forthright good, energy density is high; Simultaneously its huge specific area, has improved the load capacity of sulphur greatly, and the strong suction-operated of nano pore can realize fixing to sulphur, suppresses the loss of positive active material; Polyaniline add the loss except suppressing sulphur the also capacity that has further promoted electrode material that supplements as active material; In addition, 3-D nano, structure can provide effective conductive network and unobstructed example passage, has effectively improved specific capacity, stability and the cyclicity of secondary aluminium cell.
(4) embodiment
Below with reference to embodiment, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.The following examples have been described several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
embodiment 1:
(1) prepare vertical orientated Graphene: the nickel collector thick using 30 μ m is placed in the quartz glass tube of tube type resistance furnace as substrate, pass into argon gas and the hydrogen mixed gas of 1000sccm, wherein hydrogen volume ratio is 1%, is warming up to 650 DEG C simultaneously; Regulation voltage is to 10kV, produce stable glow plasma, remove substrate surface impurity, after 10min, pass into 150sccm methane and 1350sccm argon gas, pass into steam simultaneously, control relative humidity 40%, then stop passing into argon gas and hydrogen mixed gas, reaction 20min, after end at reducing atmosphere borehole cooling to room temperature, take out for subsequent use.
(2) composite polyphenylene amine: configuration 0.5mol/L sulfuric acid solution, to the aniline monomer that adds 0.2mol/L in this solution, passes into nitrogen and stir; The vertical orientated Graphene preparing is placed in to aniline-sulfuric acid solution and soaks 20min, then taking orientation Graphene as work electrode, saturated calomel electrode as reference electrode, platinum electrode is as to electrode, adopt cyclic voltammetry to prepare polyaniline, electro-deposition voltage is 0.7V, reaction time 1h; Finally take out product, through distilled water flushing, drying for standby.
(3) composite sulfur: by the vertical orientated graphene-polyaniline composite material preparing and elemental sulfur in mass ratio 1:10 put into tube furnace, under nitrogen atmosphere, be heated to 155 DEG C of formation combination electrodes.
(4) secondary aluminium cell preparation method: by above-mentioned composite positive pole be cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, be wound into battery core with the thick non-negative pole of knitting barrier film and make as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid that reinjects, AA type cylinder secondary aluminium cell is made in sealing.
When battery charging and discharging loop test, charge to 2.5V with 1C, 0.1C electric discharge, discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.76V, and discharge capacity is 860mAh first, and after 50 charge and discharge cycles, capability retention is 80.2%.
embodiment 2:
Prepare vertical orientated Graphene method and composite polyphenylene amine method with embodiment 1.
Composite sulfur: sulfur-bearing active material is heated to molten state; under nitrogen protection, the vertical orientated graphene-polyaniline composite material preparing is put into wherein; keep taking out after 10h that to put into baking oven dry, form vertical orientated Graphene-nano polyaniline-sulphur composite material.
Secondary aluminium cell preparation method and method of testing are with embodiment 1.
Battery open circuit voltage is 1.75V, and discharge capacity is 856mAh first, and after 50 charge and discharge cycles, capability retention is 79.8%.
embodiment 3:
Prepare vertical orientated Graphene: adopt the stainless steel-based end, enclose iron powder on its surface, be positioned in CVD (Chemical Vapor Deposition) chamber, sealing; Apply magnetic field in substrate vertical direction; magnetic field intensity is 0.01T, passes into 50sccm argon gas 30min to get rid of reaction indoor oxygen, heated substrate to 700 DEG C; then pass into 100sccm methane; keep 1h, after reaction finishes, stop heating; close methane; under argon shield, be cooled to room temperature, take out product and adopt 1mol/L hydrochloric acid cleaning, dry for standby.
Composite polyphenylene amine method is with embodiment 1, and composite sulfur method is with embodiment 2, and secondary aluminium cell preparation method and method of testing are with embodiment 1.
Battery open circuit voltage is 1.77V, and discharge capacity is 868mAh first, and after 50 charge and discharge cycles, capability retention is 81.3%.
Although the present invention is described in detail with reference to embodiment, but those skilled in the art is to be understood that, in the case of the spirit and scope of the present invention described in not departing from appended claims and equivalent thereof, can make various amendments and replacement to it.
Claims (9)
1. the coated carbon sulphur anode composite of nano polyaniline, is characterized in that, comprising:
(a) vertical orientated Graphene;
(b) conductive substrates;
(c) nano polyaniline; With
(d) sulfur-bearing active material.
2. the coated carbon sulphur anode composite of nano polyaniline as claimed in claim 1, is characterized in that, Graphene is vertically grown in conductive substrates surface.
3. the coated carbon sulphur anode composite of nano polyaniline as claimed in claim 1, it is characterized in that, described conductive substrates includes but not limited to the metals or nonmetal such as carbon fiber, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon.
4. the coated carbon sulphur anode composite of nano polyaniline as claimed in claim 1, is characterized in that, described polyaniline is to be coated on vertical orientated Graphene surface with nanoscale.
5. the coated carbon sulphur anode composite of nano polyaniline as claimed in claim 1, is characterized in that the organic compound that described sulfur-bearing active material comprises elemental sulfur or contains S-S key.
6. the coated carbon sulphur anode composite of nano polyaniline as claimed in claim 1, is characterized in that, described sulfur-bearing active material is distributed in vertical orientated Graphene with nanoscale.
7. the coated carbon sulphur anode composite of nano polyaniline as claimed in claim 1, is characterized in that, comprises 60 ~ 80% sulphur, 15 ~ 30% polyaniline and 5 ~ 10% vertical orientated Graphene, and described is mass percentage content.
8. the preparation method of the coated carbon sulphur anode composite of nano polyaniline claimed in claim 1, is characterized in that, comprises the following steps:
Step 1, prepare vertical orientated Graphene: by plasma enhanced chemical vapor deposition at the vertical orientated Graphene of conductive substrates superficial growth;
Step 2, composite polyphenylene amine: configuration 0.5mol/L sulfuric acid solution, to the aniline monomer that adds 0.2mol/L in this solution, passes into nitrogen and stir stand-by; Then taking the orientation Graphene for preparing as work electrode, saturated calomel electrode is as reference electrode, platinum electrode are as to electrode, adopts cyclic voltammetry to prepare polyaniline, its potential range is 0.6V ~ 0.8V, reaction time 1h; Finally take out product, through distilled water flushing, dry, obtain vertical orientated Graphene-nano polyaniline composite material;
Step 3, composite sulfur: adopt heat treated mode that sulphur is carried in the prepared vertical orientated Graphene-nano polyaniline composite material of step 2; Particularly, by the vertical orientated graphene-polyaniline composite material preparing and sulfur-bearing active material in mass ratio 1:5 ~ 1:20 mix, under inert gas shielding, be heated to 155 ~ 300 DEG C and form the coated carbon sulphur anode composites of nano polyaniline; Or sulfur-bearing active material is heated to molten state, under inert gas shielding, the vertical orientated graphene-polyaniline composite material preparing is put into wherein, keep taking out after 5 ~ 10h that to put into baking oven dry, form the coated carbon sulphur anode composite of nano polyaniline.
9. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
(a) the coated carbon sulphur anode composite of nano polyaniline claimed in claim 1;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410502622.4A CN104201358B (en) | 2014-09-26 | 2014-09-26 | Based on the sulphur anode composite and preparation method thereof of nano polyaniline coated graphite alkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410502622.4A CN104201358B (en) | 2014-09-26 | 2014-09-26 | Based on the sulphur anode composite and preparation method thereof of nano polyaniline coated graphite alkene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104201358A true CN104201358A (en) | 2014-12-10 |
| CN104201358B CN104201358B (en) | 2016-03-23 |
Family
ID=52086622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410502622.4A Expired - Fee Related CN104201358B (en) | 2014-09-26 | 2014-09-26 | Based on the sulphur anode composite and preparation method thereof of nano polyaniline coated graphite alkene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104201358B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322178A (en) * | 2015-10-16 | 2016-02-10 | 广东烛光新能源科技有限公司 | Electrochemical battery electrode, electrochemical battery containing same and preparation method thereof |
| CN108346520A (en) * | 2017-01-23 | 2018-07-31 | 广州墨羲科技有限公司 | Three-dimensional graphene composite material, its manufacturing method and application |
| CN108878170A (en) * | 2018-06-27 | 2018-11-23 | 东北大学 | A method of regulation ion liquid type supercapacitor power density |
| CN110246702A (en) * | 2018-03-09 | 2019-09-17 | 广州墨羲科技有限公司 | A kind of porous metals/three-dimensional graphene composite material |
| CN110690427A (en) * | 2019-10-12 | 2020-01-14 | 福建师范大学 | Preparation method of doped ternary material coated by polymeric aluminum-graphene |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090325071A1 (en) * | 2008-05-20 | 2009-12-31 | Gm Global Technology Operations, Inc. | Intercalation Electrode Based on Ordered Graphene Planes |
| CN102568853A (en) * | 2012-03-01 | 2012-07-11 | 浙江大学 | Super-capacitor electrode based on vertical oriented graphene and manufacturing method thereof |
| US20130209880A1 (en) * | 2010-11-26 | 2013-08-15 | Ulvac, Inc. | Positive Electrode for Lithium-Sulfur Secondary Battery and Method of Forming the Same |
| CN103682274A (en) * | 2013-12-19 | 2014-03-26 | 浙江师范大学 | Graphene/polyaniline/sulfur composite material and preparation method thereof |
| CN104022267A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Sandwich-structure sulfur-graphene-conductive polymer composite material, preparation and application |
| CN204088457U (en) * | 2014-09-26 | 2015-01-07 | 南京中储新能源有限公司 | The carbon sulphur anode composite that a kind of nano polyaniline is coated and secondary cell |
-
2014
- 2014-09-26 CN CN201410502622.4A patent/CN104201358B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090325071A1 (en) * | 2008-05-20 | 2009-12-31 | Gm Global Technology Operations, Inc. | Intercalation Electrode Based on Ordered Graphene Planes |
| US20130209880A1 (en) * | 2010-11-26 | 2013-08-15 | Ulvac, Inc. | Positive Electrode for Lithium-Sulfur Secondary Battery and Method of Forming the Same |
| CN102568853A (en) * | 2012-03-01 | 2012-07-11 | 浙江大学 | Super-capacitor electrode based on vertical oriented graphene and manufacturing method thereof |
| CN103682274A (en) * | 2013-12-19 | 2014-03-26 | 浙江师范大学 | Graphene/polyaniline/sulfur composite material and preparation method thereof |
| CN104022267A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Sandwich-structure sulfur-graphene-conductive polymer composite material, preparation and application |
| CN204088457U (en) * | 2014-09-26 | 2015-01-07 | 南京中储新能源有限公司 | The carbon sulphur anode composite that a kind of nano polyaniline is coated and secondary cell |
Non-Patent Citations (1)
| Title |
|---|
| 岳竞慧: ""铝二次电池离子液体电解液及介孔炭/硫正极材料的研究"", 《中国优秀硕士学位论文全文数据库（工程科技II辑）》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322178A (en) * | 2015-10-16 | 2016-02-10 | 广东烛光新能源科技有限公司 | Electrochemical battery electrode, electrochemical battery containing same and preparation method thereof |
| CN105322178B (en) * | 2015-10-16 | 2019-01-01 | 广东烛光新能源科技有限公司 | Electrochemical battery electrode, electrochemical battery containing same and preparation method thereof |
| CN108346520A (en) * | 2017-01-23 | 2018-07-31 | 广州墨羲科技有限公司 | Three-dimensional graphene composite material, its manufacturing method and application |
| CN110246702A (en) * | 2018-03-09 | 2019-09-17 | 广州墨羲科技有限公司 | A kind of porous metals/three-dimensional graphene composite material |
| CN110246702B (en) * | 2018-03-09 | 2022-05-20 | 广州墨羲科技有限公司 | Porous metal/three-dimensional graphene composite material, and manufacturing method and application thereof |
| CN108878170A (en) * | 2018-06-27 | 2018-11-23 | 东北大学 | A method of regulation ion liquid type supercapacitor power density |
| CN110690427A (en) * | 2019-10-12 | 2020-01-14 | 福建师范大学 | Preparation method of doped ternary material coated by polymeric aluminum-graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104201358B (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | High areal capacity dendrite‐free Li anode enabled by metal–organic framework‐derived nanorod array modified carbon cloth for solid state Li metal batteries | |
| CN104393233B (en) | Graphene array-based carbon-sulfur composite electrode and secondary cell | |
| CN104269539A (en) | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery | |
| CN204118182U (en) | A kind of carbon sulphur anode composite and secondary aluminium cell | |
| CN104269516B (en) | A kind of secondary cell anode composite based on vertical orientated Graphene | |
| CN104157879B (en) | A kind of secondary cell carbon sulfur anode composite | |
| CN204204953U (en) | A kind of carbon sulphur combination electrode based on graphene array and secondary cell | |
| CN104201358B (en) | Based on the sulphur anode composite and preparation method thereof of nano polyaniline coated graphite alkene | |
| CN104157829B (en) | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube | |
| CN104362290A (en) | Preparation and application of porous carbon coated orientation carbon nano tube/sulfur composite anode | |
| CN104201350A (en) | Secondary battery based on graphene aerogel/sulphur composite material | |
| CN104269543A (en) | Graphene-cladded sulfur/microporous carbon sphere composite cathode material | |
| CN204088457U (en) | The carbon sulphur anode composite that a kind of nano polyaniline is coated and secondary cell | |
| CN109755554A (en) | A kind of aluminium selenium secondary cell | |
| CN104078680B (en) | A kind of carbon sulphur anode composite and secondary aluminium-sulfur battery | |
| CN104183835A (en) | Aluminium carbon aerogel composite material and secondary battery adopting aluminium carbon aerogel composite material as negative electrode | |
| CN104157878A (en) | Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof | |
| CN104300127A (en) | Sulfur-based composite material coated with carbon, preparation and application thereof | |
| CN204243148U (en) | A kind of secondary cell combination electrode and secondary aluminium cell | |
| CN104183850A (en) | Carbon-sulphur composite electrode based on carbon nano tube arrays as well as preparation method and application of carbon-sulphur composite electrode | |
| CN204130629U (en) | A kind of secondary aluminium cell graphene array anode composite | |
| CN104201352A (en) | Preparation and application of carbon-sulfur composite positive electrode based on CNT (carbon nano tube) sponge | |
| CN104078678A (en) | Sulfur-carbon conductive polymer positive electrode and secondary aluminium battery using same | |
| CN104362313A (en) | Polypyrrole, mesoporous carbon and sulfur composite electrode material and secondary cell | |
| CN104269544B (en) | Graphene array anode composite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160323 Termination date: 20190926 |